Photocatalytic Composition for Water Purification

ABSTRACT

The present invention refers to lightweight and settable photocatalytic compositions and solid composites; methods of preparing the compositions and solid composites; and their use in water purification. The compositions are comprised of photocatalysts such as titanium dioxide (TiO 2 ) and zinc oxide (ZnO), lightweight glass bubbles, and a hydraulic cementing binder. The lightweight and settable photocatalytic compositions can be formed into lightweight photocatalytic solid composites and/or structures by mixing with water and moist curing. This invention also describes relatively simple, fast, and cost effective methodologies to photodope the TiO 2 —ZnO compositions and composites with silver (Ag), to enhance and extend the photocatalytic activity from the ultraviolet into the visible light spectrum. The lightweight and settable TiO 2 —ZnO and Ag—TiO 2 —ZnO compositions are used in making solids, structures, coatings, and continuous or semi-continuous water purification panels for purifying contaminated water.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional PatentApplication No. 61/747,629, filed Dec. 31, 2012.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

Not Applicable

THE NAMES OF THE PARTIES TO A JOINT RESEARCH AGREEMENT

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REFERENCE TO SEQUENCE LISTING, A TABLE, OR A COMPUTER PROGRAM LISTINGCOMPACT DISC APPENDIX

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TECHNICAL FIELD

The present invention is in the field of photocatalysis. Moreparticularly, the present invention is in the technical field ofphotocatalytic compositions, composites, and methods for waterpurification.

BACKGROUND OF THE INVENTION

Clean and safe water is an indispensable resource essential for thesurvival of all species. Although 70% of the Earth is covered by water,only 2.5% of this is freshwater. Most of that water is unattainable,which leaves less than 1% of the Earth's freshwater for humanconsumption. According to the World Health Organization, one-sixth ofthe global population lacks access to clean drinking water. It wouldgreatly benefit society, and save millions of lives, if we had safe,affordable, sustainable and easily deployable water purificationtechniques. Drinking water contamination can come from harmfulmicrobiological pathogens, organic chemicals and heavy metals. Currentwater purification techniques include filtration, chemical means such aschlorination, ozonation, aeration, reverse osmosis, and ultraviolet (UV)radiation using UV-Clamps (operating at wavelength in the range 100-280nm). Some of the above mentioned water purification techniques use lampsand require electricity to operate, some use slow physical separationprocesses, and others use chemicals that generate compounds leading tosecondary pollution and even leave water with a bad smell and aftertaste. There is a pressing need for green, sustainable, easy to use,inexpensive and effective technologies for water purification.

Ultraviolet radiation from the sun (UV-A, wavelength of 315-400 nm) is asafe and cost-effective means to purify water infected bymicrobiological pathogens such as bacteria. When UV strikes thedeoxyribonucleic acid (DNA) of bacteria, pyrimidine dimers or bonds areformed between adjacent thymine or cytosine base pairs. This inactivatesthe bacteria by preventing its DNA from replicating. Since the moreharmful UV-B and UV-C radiation from the sun are blocked by theatmosphere, solar disinfection, commonly referred to as SODIS, thatprimarily uses UV-A radiation is very slow. In recent yearsphotocatalysts such as TiO₂ and ZnO, have been used to accelerate thephotocatalytic SODIS process.

A photocatalyst is a substance, that when activated by light radiation(UV-A radiation and/or visible light, in the present invention),increases the rate of a reaction, without itself being consumed in thereaction. Anatase crystalline TiO₂ and ZnO are photocatalysts that areactivated by UV-A radiation from the sun. When UV-A radiation strikesthese photocatalysts, electrons from the valence band are energized intothe conduction band (e⁻) thereby leaving holes or positive charges (h⁺)in the valence band. Some of the electrons and holes may recombine, butmost combine with oxygen and water to create reactive oxygen speciessuch as super oxides (O₂ ⁻), hydroxyl radicals (.OH) and hydrogenperoxide (H₂O₂). These reactive species are responsible for thephoto-killing of bacteria, reduction of heavy metals, and oxidation (anddegradation) of organics into harmless species. The highly reactiveoxygen species destroy pathogens by damaging cellular membranes, lipids,proteins and mitochondria. They also disrupt their DNA, alter theirstructure and prevent them from replicating.

One of the problems associated with the use of TiO₂ for waterpurification, is the difficulty in recovering the TiO₂ nanoparticles byfiltration from the TiO₂-water slurry, after the disinfection process.The slurry also impedes the transmission of UV, especially since TiO₂and ZnO are typically used in sunscreens to block UV radiation from thesun. In one of the field applications that use TiO₂ assisted SODIS, TiO₂is mixed with perchloric acid and coated in the inner surface of plasticPolyethylene terephthalate (PET) water bottles. The bottles are filledwith contaminated water and exposed to the sun, to be purified byphotocatalysis. The primary drawback of this method is that thenon-uniform TiO₂ coatings block UV radiation which diminishesphotocatalytic activity. Another drawback of this method is that theTiO₂ coatings often wash-off after repeated use. Yet another limitationof the existing TiO₂ enhanced SODIS method is its reduced efficiencywhen UV index is very low, since it uses UV-A radiation which comprisesonly 3% of the solar energy.

DESCRIPTION OF THE PRIOR ART

U.S. Pat. No. 7,556,683 describes a photocatalytic granular mixture formortar and concrete and their use in the fields of construction orrenovation of buildings, or roadway coatings for imparting propertiesfor self-cleaning, reduction of odors, and depollution of ambient air.The photocatalytic granular mixture of titanium oxide particlescomprises titanium oxide particles of n granular classes havingdifferent specific surface areas, n being a number greater than or equalto 2. The photocatalytic granular mixture can be in the form of a powderor in the form of an aqueous solution containing a dispersing agent,compatible with the cement, concrete and mortar media.

US2010/0137130 describes a composition that is photocatalytically activeand comprises coating carrier material particles with photocatalyticallyactive particles. The composition is prepared using high energy mixingand the coating is performed in the presence of a hydraulic medium. Thephotocatalytically active composition has low dusting characteristicsand good flow ability and is suitable for use in concrete or mortarmixes for preparing structures and materials for maintaining a cleansurface.

EP0923988B1 discloses a photocatalyst-carrying structure comprising aphotocatalyst layer, held by an adhesive layer to a substrate, whereinthe adhesive layer is composed of silicon-modified resin,polysiloxane-containing resin or colloidal silica-containing resin.Materials such as glass, plastics, metals, fabrics, and wood materials,carrying the photocatalyst-carrying structure with a photocatalyst isresistant to deterioration and is highly durable.

U.S. Pat. No. 7,211,543 describes a photocatalyst composition whichcomprises modified photocatalyst particles and a binder componentcomprising a phenyl group-containing silicone and optionally an alkylgroup. The photocatalyst particles are prepared by subjecting particlesof a photocatalyst to a modification treatment comprising at least onemodifier compound selected from the group consisting of differentcompounds consisting of a triorganosilane unit, a monooxydiorganosilaneunit and a dioxyorganosilane unit. The invention also describes a filmformed using the photocatalyst composition and a shaped article producedby shaping the photocatalyst composition.

EP0812619 discloses a photocatalytic homogeneous gel compositiontransparent to visible and/or solar radiation, comprising titaniumdioxide and cerium oxide photocatalysts, dispersed in an aluminosilicateinorganic polymer binder of the Imogolite type. The composition may becoated on a photocatalytic element such as an organic or glass polymersupport. The patent also provides a method to destroy organics in anaqueous solution by making the solution to flow over the photocatalyticelement.

U.S. Pat. No. 5,547,823 describes a process for making photocatalystcomposite comprising photocatalyst such as TiO₂, adhered to a substrateby a less degradative adhesive such as fluorinated polymer. Thecomposite may be used for removal of deleterious and malodorousmaterials, bacteria, fungi, algae and the like. This patent alsodiscloses a coating composition comprising a dispersion of photocatalystand adhesive in a solvent.

U.S. Pat. No. 5,275,741 describes a method for the photocatalytictreatment of aqueous mixtures of polluting substances by radiations froma lamp emitting radiations with a wavelength shorter than 400 nm. Themethod comprises irradiating the polluted aqueous mixtures in thepresence of titanium dioxide, while the mixtures are circulating insidea reactor.

SUMMARY OF THE INVENTION

The first aspect of this invention includes simple, fast, and costeffective methodologies to synthesize a lightweight and settablephotocatalytic composition comprising photocatalysts, glass bubbles, anda settable hydraulic cementing binder. The invention also includes amethod for photodoping this composition in order to extend thephotocatalytic activity. The invention further includes a method forpreparing a lightweight photocatalytic solid composite as well as aphotodoped lightweight solid composite and the use of these compositionsand composites in water purification.

The lightweight and settable photocatalytic composition may include asingle photocatalyst or a combination of photocatalysts, such as TiO₂and ZnO, that when subjected to UV light, results in electron transitionfrom the valence band to the conduction band of the material, therebyleaving hole in the valence band. The method for preparing thelightweight and settable photocatalytic composition involves firstproportioning, mixing and blending the photocatalysts in apre-determined ratio, such as a ratio of ZnO:TiO₂ of 1:4. Thenpre-determined amounts of lightweight glass bubbles and hydrauliccementing binder are added in stages and mixed by mechanical means.Several proportions by weight of ZnO:TiO₂:glass bubbles:cementingbinder, such as 1:4:25:100, can be used in the composition as long asthe compositions retain their photocatalytic properties.

The photocatalysts in the lightweight and settable composition mayfurther be doped with non-metals or metals in order to extend thephotocatalytic activity from the ultraviolet into the visible lightspectrum. The method for photodoping the photocatalytic composition withdopants such as Ag involves first mixing or coating the photocatalystsand/or photocatalytic composition with a metal salt solution, such as0.1 M silver nitrate (AgNO₃), and exposing it to the sun. Then thephotodoped photocatalysts and/or photocatalytic composition is calcinedat temperatures between 200° C. and 500° C. for a period of 1 to 3hours.

The lightweight and settable photocatalytic compositions can be formedinto lightweight photocatalytic solid composites and/or structures bymixing with water and moist curing. The surface of the lightweight solidcomposites may be photodoped with a metal salt, such as Ag, as describedpreviously. The lightweight TiO₂—ZnO and Ag—TiO₂—ZnO photocatalyticsolid composites may be cast into any form that can be placed in contactwith water and exposed to sunlight or artificial light, until thecontaminated water is purified by photocatalysis. Photocatalytic spheresand cylinders that can be placed in water vessels, a water tank, and acontinuous or semi-continuous water purification panel, were developedfor easy deployment of the invention, without blocking light and withoutwashing-off.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a flow chart illustrating the separate steps forsynthesizing the lightweight and settable TiO₂—ZnO photocatalyticcomposition.

FIG. 2 shows a flow chart illustrating the separate steps forsynthesizing the lightweight and settable Ag—TiO₂—ZnO photocatalyticcomposition.

FIG. 3 shows a flow chart illustrating the separate steps forsynthesizing the lightweight TiO₂—ZnO photocatalytic solid composite.

FIG. 4 shows a flow chart illustrating the separate steps forsynthesizing the lightweight Ag—TiO₂—ZnO photocatalytic solid composite.

FIG. 5A shows a perspective view and FIG. 5B shows a side view ofvarious substrates or solids that are coated with the lightweight andsettable photocatalytic composition.

FIG. 6 shows a cylindrical photocatalytic rod made with the lightweightand settable photocatalytic composition, immersed in water inside a PETwater bottle.

FIG. 7 shows a water tank coated with the lightweight and settablephotocatalytic composition.

FIG. 8 shows a water purification panel made using the lightweightphotocatalytic composite spheres placed in UV and visible lighttransparent tubes, and parabolic trough reflectors to concentratesunlight on the photocatalytic composite.

FIG. 9A shows the SEM and FIG. 9B shows the EDS results for thelightweight TiO₂—ZnO photocatalytic solid composite.

FIG. 10A shows the SEM and FIG. 10B shows the EDS results for thelightweight Ag—TiO₂—ZnO photocatalytic solid composite.

FIG. 11 shows a graphical illustration of the average number ofEnterobacteriacea counts at various time intervals for the control,TiO₂—ZnO and Ag—TiO₂—ZnO solid composites exposed to sunlight in FIG.11A, visible light in FIG. 11B, and the dark in FIG. 11C.

FIG. 12 shows a graphical illustration of the average number of aerobicbacteria counts at various time intervals for the control, TiO₂—ZnO andAg—TiO₂—ZnO solid composites exposed to sunlight in FIG. 12A, visiblelight in FIG. 12B, and the dark in FIG. 12C.

FIG. 13 illustrates the mechanism of forming reactive oxygen species asa result of UV-A activated photocatalysis of the TiO₂—ZnO composite.

FIG. 14 illustrates the enhanced photocatalytic activity of theAg—TiO₂—ZnO composite and the formation of a greater number of reactiveoxygen species as a result of the synergistic effects of UV-Visphotocatalysis.

DETAILED DESCRIPTION OF THE INVENTION

As we strive for a green and environmentally-friendly world,conventional techniques for water purification must move towards greenand sustainable alternatives. Realizing this need for eco-friendly,sustainable, cost-effective, and efficient water purification systems,the inventor has developed lightweight and settable photocatalyticcompositions, comprised of photocatalysts, hollow glass bubbles, and ahydraulic cementing binder. The inventor has also developed methods todeploy and use the lightweight and settable photocatalytic compositionin systems for purifying water.

The photocatalyst used in the lightweight and settable composition maybe either a single photocatalyst or combination of photocatalysts, whichare selected from materials such as TiO₂, ZnO, WO₃, Cu₂O, SnO₂, SiO₂,RuO₂, SrTiO₃, Fe₂O₃, NiO, SiC, and the like, that when subjected tolight, results in transition of electrons from the valence band to theconduction band of the material, thereby leaving holes in the valenceband. These electrons and holes participate in advanced oxidation andreduction reactions. The photocatalysts used in the lightweight andsettable composition may also include non-metals and metals such as N,C, S, P, B, F, I, Cu, Ag, Pt, Pd, Mn, Wo, Ni, Sn, Fe, V and the like, ortheir oxides as dopants, to enhance and extend its photocatalyticactivity from the ultraviolet into the visible light spectrum.

The glass bubbles used in the present invention include all types ofcommercially available glass bubbles or hollow glass microspheres thatare typically made of sodium silicate, aluminosilicate, or borosilicatematerials. The glass bubbles are transparent to UV and visible light andhave sizes ranging from 100 nanometers to 5 millimeters in diameter. Theglass bubbles used in the lightweight and settable photocatalyticcomposition of the present invention had median particle size rangingfrom 15 microns to 70 microns. Glass bubbles of any other size range mayalso be used. The glass bubbles are hollow and light weight, withdensities ranging from 0.1 to 0.7 g/cc. Hence, by increasing ordecreasing the amount of glass bubbles in the composition, they areuseful in creating solid photocatalytic composites that can be made tofloat or sink in water. The inclusion of glass bubbles in thephotocatalytic composition also increases the flow of the dryphotocatalytic composition and also increases the workability of themixture as water is added to the photocatalytic composition in order toprepare solid composites. This increase in workability as measured bythe slump test (as described in ASTM C143/C143M) assists in easyplacement, compaction, and coating.

The settable hydraulic cementing binder in the lightweight and settablephotocatalytic composition commonly comprises of all types of Portlandcements, blended hydraulic cements, performance based hydraulic cements,special cements, and combinations thereof. When water is added to thecement, it chemically reacts with the hydraulic binding material in areaction known as hydration, and results in a paste that sets andhardens with time. This property allows cement to be used as a bindingmaterial in the manufacture or production of concrete.

Lightweight and Settable Photocatalytic Composition: The invention alsoprovides a method for preparing a light weight and settablephotocatalytic composition, in which the proportions by weight ofZnO:TiO₂:glass bubbles:cementing binder, is for example in the ratio of1:4:25:100. Various other photocatalysts and mixing ratios can be usedas long as the composition retains its photocatalytic properties. Ingeneral, the photocatalytic activity increases with the type and amountof photocatalyst in the lightweight and settable photocatalyticcomposition. The method for preparing the lightweight and settablephotocatalytic composition (FIG. 1) comprises proportioning, mixing andblending the photocatalysts in pre-determined ratios (if there are morethan one photocatalyst, such as ZnO and TiO₂). This is followed by theaddition of the pre-determined amount of lightweight glass bubbles, andmixing by mechanical means such as hand agitation or rolling in ahorizontal ball mill, wherein the glass bubbles also act as tiny ballsin the rotating ball mill, resulting in a homogenous mixture ofphotocatalysts and glass bubbles. A pre-determined amount of hydrauliccementing binder is added next and the mechanical mixing is continuedfor 5 to 10 minutes, until a homogenous lightweight and settablephotocatalytic composition is formed (for example a lightweight andsettable TiO₂—ZnO composition of the present invention).

Doping TiO₂ with Ag is known to extend the photocatalytic range of TiO₂,from UV into the visible light spectrum. Ag is also a well-knownbactericide that can aid in water purification. The inventor developed arelatively simple, fast, and cost effective methodology, to synthesize anovel lightweight and settable UV-Vis photocatalytic composition(Ag—TiO₂—ZnO) by photodoping the TiO₂—ZnO composition described earlier.The doping process of this invention (FIG. 2), referred to asphotodoping, comprises mixing the photocatalysts and/or photocatalyticcomposition with a metal salt solution, such as 0.1M AgNO₃, and thenexposing this to the sun. This is followed by calcining the Ag dopedphotocatalysts or photocatalytic composition at temperatures between200° C. and 500° C. for a period of 1 to 3 hours. The lightweight andsettable photocatalytic composition may further comprise additives oradmixtures typically used in cement mortar or cement concrete for rapidhardening, improve workability, air entrainment, or color. Thephotodoping method described in this invention is fast, simple and costeffective compared to the time consuming and arduous sol-gel techniquesreported in literature.

Lightweight Photocatalytic Solid Composite: This lightweight andsettable photocatalytic composition may be used as an additive for dryor wet mortar formulation. The photocatalytic composition may be mixedwith water to form a paste for coating photocatalytically activesurfaces, or for binding aggregates together in the production ormanufacture of concrete. When water is added to the photocatalyticcomposition, it chemically reacts with the hydraulic binding material ina reaction known as hydration, resulting in a paste that sets andhardens with time. The hardening and strength gain with time requiresmoisture curing for a period of 7 to 28 days or even more, depending onthe type of hydraulic cementing binder used in the formulation. Afterhardening, the photocatalysts are tightly bound to the solidphotocatalytic composite, and do not wash-off after repeated use. Theamount of water to be added is commonly referred as the“water-cementitious materials ratio” or simply as the “water-cementratio”. It is the ratio of the mass of water to mass of hydrauliccementing binder. The water-cement ratio to be used depends on theparticular application and the desired properties of the hardenedconcrete; it is typically kept between 0.40 and 0.50 for engineeringconstruction. High water-cement ratio results in low strength ofhardened concrete. However, if the water-cement ratio is too low, theworkability is reduced and it becomes difficult to mix, place andcompact the fresh concrete. The inclusion of glass bubbles in thephotocatalytic composition, improves the workability of mortar or freshconcrete, and thereby enables the use of low water-cement ratio (below0.40) without impacting strength.

To prepare the lightweight TiO₂—ZnO photocatalytic solid composites(FIG. 3), the lightweight and settable photocatalytic composition ismixed with water at the appropriate water-cement ratio (and optionallymixed with other aggregates such as sand and gravel). The resulting mixis placed and compacted in molds or of any desired shape or form(spherical, cubical, cylindrical etc.). The mixture is the allowed toset and harden with time. This time may vary from 7 to 28 days or evenmore, depending on the hydraulic cementing binder used. After settingand hardening a lightweight solid photocatalytic composite is formed. Byincreasing or decreasing the amount of the light weight (density 0.2g/cc) glass bubbles in the composition, the lightweight solidphotocatalytic composite could be made to float (composite density<1.0g/cc), or sink (composite density>1.0 g/cc) in water.

The invention also provides a relatively simple, fast, and costeffective methodology, to synthesize lightweight, Ag—TiO₂—ZnOphotocatalytic solid composites (FIG. 4) by surface-doping thelightweight TiO₂—ZnO photocatalytic solid composite (described earlier)with minute amounts of Ag (<1 wt. %), only on the surface. The methodfor surface doping involves, spraying, brushing or coating by any othermeans the surface of the lightweight TiO₂—ZnO photocatalytic solidcomposites with a metal salt solution, such as 0.1M AgNO₃, and exposingit to the sun. The photocatalytic composite turns dark as Ag getsphotoreduced onto the surface of the composite. The Ag doped compositeis further calcined at temperatures between 200° C. and 500° C. for aperiod of 1 to 3 hours, to form the lightweight Ag—TiO₂—ZnOphotocatalytic solid composite.

APPLICATIONS

The lightweight photocatalytic solid composites developed in thisresearch can be easily deployed in several different ways to avoid thedrawbacks of conventional TiO₂ enhanced SODIS methods (namely theblocking of UV rays and washing off after repeated use). In oneembodiment, various substrates or solids can be coated with thelightweight and settable photocatalytic compositions 1 (FIG. 5) and maybe placed in contact with contaminated water in vessels or containers 2that are transparent to UV and visible light (such as PET waterbottles), and exposed to sunlight or artificial, until the contaminatedwater is purified (FIG. 6).

In another embodiment, lightweight photocatalytic concrete water tanksmay be constructed with the lightweight and settable photocatalyticcomposition mixed with concrete, or existing water tanks can be coatedwith the lightweight and settable photocatalytic composition (FIG. 7).Contaminated water may then be treated in the photocatalytic tanks byexposure to sunlight (or artificial light) to purify water, before use,or even before being discharged to lakes, streams, rivers and otherwater bodies. This could reduce the use of harsh chemicals for treatingwater.

In yet another embodiment, the lightweight photocatalytic solidcomposite may be deployed in a continuous or semi-continuous waterpurification system that could be built as a small residentialpoint-of-use system, or built on a larger scale for batch waterpurification (FIG. 8). A photocatalytic water purification panel isconstructed out of UV and visible light transparent tubes 3 such asPolyethylene terephthalate glycol-modified (PETG), acrylic, glass, orany other tubes that are transparent to UV and visible light. The tubesmay be interconnected in series using elbows and connectors 4. Thelightweight photocatalytic solid composites 5 (spheres, cubes, cylindersor of any size, shape or form) are placed in the tubes; parabolic troughreflectors 6 made of solar reflector film may be used to concentratesunlight on the photocatalytic composite contained in the tubes. Thetubes are filled with contaminated water through the inlet 7 and areexposed to sunlight until the water is purified by photocatalysis. Thewater purification panel can be built large enough to treat water in abatch process. The water purification panel may be filled with a newbatch of contaminated water and the purification process can becontinued. For a continuous flow water purification system, the flowrate can be reduced by a flow control valve 8 so that water remains inthe system for a sufficient amount of time, until purified.

EXAMPLES

Materials: The raw materials used in synthesizing the photocatalyticcomposites were commercially available Portland cement, K20 glassbubbles having soda-lime-borosilicate glass composition from 3M Center,TiO₂ Degussa (P-25) with 80% anatase and 20% rutile crystal structure,ZnO and AgNO₃ from Fisher Scientific. The synthesized photocatalyticcomposites were characterized by scanning electron microscopy (SEM) andenergy-dispersive X-ray spectroscopy (EDS) using a field-emissionscanning electron microscope. Enterobacteriaceae and aerobic bacteriacounts were determined using 3M Petrifilms. 3M Solar Mirror Film-1100was used in the fabrication of the prototype photocatalytic waterpurification panel.

A lightweight and settable photocatalytic composition was prepared usingtwo photocatalysts (TiO₂ and ZnO), glass bubbles, and rapid hardeningPortland cement as described earlier. A ratio of 1:4:25:100 was used forZnO:TiO₂:glass bubbles:cement. Water was added to the photocatalyticcomposition, at a water cement ratio of 0.3 and mixed using a mechanicalstirrer. The moist composition was formed into 17 mm. diameter spheresand moist cured for 7 days. After setting and hardening of the resultingmixture, the photocatalysts were tightly bound to the lightweightTiO₂—ZnO solid composite spheres. The lightweight Ag—TiO₂—ZnO solidcomposite spheres were formed by spray coating the lightweight TiO₂—ZnOcomposite spheres with 0.1 M AgNO₃ solution prepared in distilled water.The Ag—TiO₂—ZnO photocatalytic spheres were then exposed to sunlight forone hour. The TiO₂—ZnO spheres turned dark in just minutes. This changein color occurred as Ag was reduced onto the surface of the TiO₂—ZnOphotocatalytic spheres. The Ag doped composite was then calcined at atemperature of 300° C. for three hours.

Characterization of the lightweight photocatalytic solid composites: SEMand EDS results for the lightweight TiO₂—ZnO and Ag—TiO₂—ZnOphotocatalytic solid composites are shown in FIGS. 9-10. The SEM resultsof the TiO₂—ZnO composite (FIG. 9A) clearly show the glass bubblesembedded in the matrix of cement, TiO₂ and ZnO. The peaks in the EDSresults (FIG. 9B) clearly show the presence of Ti, Zn, O and variouselements that are part of the lightweight and settable composition ofPortland cement and the glass bubbles. Due to significant contrast, thepresence of Ag can be clearly seen as dark shades in the SEM image ofthe Ag—TiO₂—ZnO composite (FIG. 10A). The elemental composition by EDSconfirmed the presence of Ag in the Ag—TiO₂—ZnO composite (FIG. 10B).

Exposure studies to evaluate bacterial inactivation: The water used fortesting was obtained just after the secondary treatment, but before theaddition of sodium hypochlorite (that kills harmful bacteria) from awastewater treatment facility. Three 100 mL samples were taken in glassbeakers. A TiO₂—ZnO sphere was placed in one of the sample beakers, anAg—TiO₂—ZnO sphere was placed in the second sample beaker, and a controlcontaining only the test water sample was placed in the third samplebeaker. The photocatalytic bactericidal properties of the TiO₂—ZnO andAg—TiO₂—ZnO lightweight composites were evaluated under various exposureconditions: sunlight (outside), visible light (inside a room), and inthe dark (in a dark room).

Enterobacteriaceae counts (EBC) and aerobic bacteria counts (ABC) weredetermined with 3M Petrifilms after 0 h, 1 h, 2 h, 4 h, 6 h and 8 h. Thepetrifilms were plated (inoculated) with 1 mL of water sample. Ten-foldserial dilutions were performed for samples with high concentrations ofbacteria. The plates were incubated for 48 hours at 34° C. for the ABC,and 24 hours at 34° C. for the EBC. The colonies were then manuallycounted.

FIG. 11 shows the average number of EBC at various time intervals forthe three test samples (control, TiO₂—ZnO, Ag—TiO₂—ZnO) exposed tosunlight, visible light and in the dark. The tests were all done intriplicate. The EBC for the samples exposed to sunlight (FIG. 11A)dropped from initial average values of 197 to 0 cfu/mL in one hour forthe Ag—TiO₂—ZnO composite, 187 to 0 cfu/mL in four hours for theTiO₂—ZnO composite and 207 to 0 cfu/mL in eight hours for the control(plain SODIS) sample. The EBC for the samples exposed to visible light(FIG. 11B) dropped from initial average values of 190 to 0 cfu/mL infour hours for the Ag—TiO₂—ZnO composite, 210 to 193 cfu/mL for theTiO₂—ZnO composite and 170 to 163 cfu/mL for the control, both in eighthours. The EBC for the sample with the Ag—TiO₂—ZnO composite kept in thedark, dropped from an initial average value of 193 to 0 cfu/mL in eighthours (inactivated bacteria even in the dark), whereas the TiO₂—ZnOcomposite and the control showed no appreciable change (<10%) in the EBC(FIG. 11C).

FIG. 12 shows the average number of ABC at various time intervals forthe three test samples exposed to sunlight, visible light and in thedark. The ABC for the samples exposed to sunlight (FIG. 12A) droppedfrom initial average values of 3767 to 0 cfu/mL in one hour for theAg—TiO₂—ZnO composite, 4200 to 173 cfu/mL in eight hours for theTiO₂—ZnO composite and 3967 to 187 cfu/mL in eight hours for the controlsample. The ABC for the samples exposed to visible light (FIG. 12B)dropped from initial average values of 4067 to 0 cfu/mL in eight hoursfor the Ag—TiO₂—ZnO composite, 3933 to 3567 cfu/mL and 3967 to 3767cfu/mL for the TiO₂—ZnO composite and control respectively, both ineight hours. The ABC for the sample with the Ag—TiO₂—ZnO composite keptin the dark, dropped from an initial average value of 3900 to 287 cfu/mLin eight hours (worked even in the dark), whereas the TiO₂—ZnO compositeand the control showed no appreciable change (<10%) in the ABC (FIG.12C).

The TiO₂—ZnO composite exposed to sunlight showed 100% inactivation ofEnterobacteriaceae in 4 hours, and 96% inactivation of aerobic bacteriain 8 hours. The bacterial inactivation by the TiO₂—ZnO composite wasprimarily due to UV-A activated photocatalysis as shown by its efficacyin destroying bacteria when exposed to sunlight. There was nosignificant bacterial inactivation when exposed to visible light or inthe dark (<10%). The Ag—TiO₂—ZnO composite showed 100% inactivation ofEnterobacteriaceae and aerobic bacteria in 1 hour. Under visible light,the Ag—TiO₂—ZnO composite showed 100% inactivation of Enterobacteriaceaein 4 hours and 100% inactivation of aerobic bacteria in 8 hours, whereasthe TiO₂—ZnO and control showed no appreciable (<10%) bacterialinactivation. Even for tests performed in the dark, 100% inactivation ofEnterobacteriaceae was achieved in 8 hours, and 93% aerobic bacterialinactivation in 8 hours, whereas the TiO₂—ZnO and control showed noappreciable bacterial inactivation (<5%). The control (plain SODIS)showed 100% and 95% inactivation of Enterobacteriaceae and aerobicbacteria respectively, when exposed to UV-A; however, it took 8 hours toachieve this disinfection.

The photo-killing property of the lightweight TiO₂—ZnO composite isprimarily due to the reactive oxygen species (hydroxyl radical, superoxides and hydrogen peroxide) that are generated as a result of UV-Aactivated photocatalysis (FIG. 13) and its interaction with the cellstructure and DNA of bacteria. In the lightweight Ag—TiO₂—ZnO composite,the photocatalytic activity is greatly improved resulting in theformation of more reactive oxygen species (FIG. 14). The bactericidalpotency of the lightweight Ag—TiO₂—ZnO composite was the greatest whenexposed to sunlight, followed by visible light and finally in the dark.The synergistic effects of UV-Vis photocatalysis due to the lowering ofband-gap energy, inhibition of electron-hole recombination, and theinherent antimicrobial properties of Ag enhanced the bactericidalpotency of the novel Ag—TiO₂—ZnO composite. Thus, the novel Ag—TiO₂—ZnOlightweight composite can be used to purify water round-the-clock.

I claim:
 1. A lightweight and settable photocatalytic compositioncomprising photocatalysts such as TiO₂ and ZnO, glass bubbles, and asettable hydraulic cementing binder; method for preparing thecomposition; and its use in water purification.
 2. A compositionaccording to claim 1, wherein the photocatalyst may be a singlephotocatalyst or combination of photocatalysts which are selected frommaterials such as TiO₂, ZnO, WO₃, Cu₂O, SnO₂, SiO₂, RuO₂, SrTiO₃, Fe₂O₃,NiO, SiC, and the like, and may also include non-metals and metals suchas N, C, S, P, B, F, I, Cu, Ag, Pt, Pd, Mn, Wo, Ni, Sn, Fe, V and thelike, or their oxides as dopants, to enhance and extend itsphotocatalytic activity from the ultraviolet into the visible lightspectrum.
 3. A composition according to claim 1, in which the glassbubbles are transparent to UV and visible light, hollow and lightweight,with median particle size ranging from 15 to 70 microns and densitiesranging from 0.1 to 0.7 g/cc.
 4. A composition according to claim 1, inwhich the settable hydraulic cementing binder commonly comprises of alltypes of Portland cements, blended hydraulic cements, performance basedhydraulic cements, special cements, and combinations thereof.
 5. Acombination of photocatalysts according to claim 2, wherein thephotocatalysts are TiO₂ and ZnO.
 6. A composition according to claim 1,in which the proportions by weight of ZnO:TiO₂:glass bubbles:cementingbinder, is in the ratio of 1:4:25:100, or in various other mixing ratiosthat retain the photocatalytic properties of the composition.
 7. Amethod for preparing lightweight and settable TiO₂—ZnO and Ag—TiO₂—ZnOphotocatalytic compositions comprising: a. proportioning, mixing andblending the photocatalysts in a pre-determined ratio, such as a ratioof ZnO:TiO₂ of 1:4; b. adding pre-determined amounts of lightweightglass bubbles, and mixing by mechanical means such as hand agitation orrolling in a horizontal ball mill, wherein the glass bubbles also act astiny balls in the rotating ball mill, resulting in a homogenous mixtureof photocatalysts and glass bubbles; c. adding pre-determined amounts ofhydraulic cementing binder and mixing by mechanical means for 5 to 10minutes, until a homogenous lightweight and settable TiO₂—ZnOphotocatalytic composition is formed; d. photodoping the lightweight andsettable photocatalytic composition with dopants such as Ag by mixing orcoating the photocatalysts and/or photocatalytic composition with ametal salt solution, such as 0.1 M silver nitrate, exposing it to thesun, and calcining the photodoped photocatalysts and/or photocatalyticcomposition at temperatures between 200° C. and 500° C. for a period of1 to 3 hours to form a lightweight and settable Ag—TiO₂—ZnOphotocatalytic composition.
 8. A lightweight and settable photocatalyticcomposition according to claim 7, in which the photocatalyticcomposition further comprises additives or admixtures for rapidhardening, improve workability, air entrainment, or color.
 9. A wetmortar formulation comprising the photocatalytic composition of claim 7,for coating applications and/or for binding aggregates in thepreparation of lightweight photocatalytic concrete.
 10. A method forpreparing lightweight TiO₂—ZnO and Ag—TiO₂—ZnO photocatalytic solidcomposites and/or structures by: a. preparing lightweight TiO₂—ZnOphotocatalytic solid composite by mixing with water at the appropriatewater-cement ratio and compacting in molds of any desired shape or form;b. coating the surface of the said TiO₂—ZnO photocatalytic solidcomposite with 0.1M silver nitrate, exposing it to the sun, andcalcining the photodoped composite at temperatures between 200° C. and500° C. for a period of 1 to 3 hours thereby creating a lightweightAg—TiO₂—ZnO photocatalytic solid composites.
 11. A method of castinglightweight TiO₂—ZnO and Ag—TiO₂—ZnO photocatalytic solid compositesaccording to claim 10, into solid spheres, cubes, cylinders or of anyregular or irregular size, shape or form, that may be placed in contactwith water and exposed to sunlight or artificial light, until thecontaminated water is purified by photocatalysis.
 12. A water vesselcontaining the lightweight TiO₂—ZnO and Ag—TiO₂—ZnO photocatalytic solidcomposites of claim 10, for purifying water.
 13. A water purificationpanel containing the lightweight TiO₂—ZnO and Ag—TiO₂—ZnO photocatalyticsolid composites of claim 10, and its use in water purification,comprising: a. tubes transparent to sunlight or artificial light,containing the lightweight TiO₂—ZnO and Ag—TiO₂—ZnO photocatalytic solidcomposites; b. parabolic trough reflectors to concentrate sunlight orartificial light on the lightweight TiO₂—ZnO and Ag—TiO₂—ZnOphotocatalytic solid composites contained in the tubes; c. filling thetubes with contaminated water and exposing to sunlight or artificiallight until the water is purified.
 14. A method of purifyingcontaminated water inside a lightweight reinforced concrete water tanks,constructed or coated with the lightweight and settable TiO₂—ZnO andAg—TiO₂—ZnO photocatalytic compositions according to claim 7.